Mechanism of Proton Transport in Ionic-Liquid-Doped Perfluorosulfonic Acid Membranes

Abstract

Ionic-liquid-doped perfluorosulfonic acid membranes (PFSA) are promising electrolytes for intermediate/high-temperature fuel cell applications. In the present study, we examine proton-transport pathways in a triethylammonium-triflate (TEATF) ionic liquid (IL)-doped Nafion membrane using quantum chemistry calculations. The IL-doped membrane matrix contains triflic acid (TFA), triflate anions (TFA–), triethylamine (TEA), and triethylammonium cations (TEAH+). Results show that proton abstraction from the sulfonic acid end groups in the membrane by TFA– facilitates TEAH+ interaction with the side-chains. In the IL-doped PFSA membrane matrix, proton transfer from TFA to TEA and TFA to TFA– occurs. However, proton transfer from a tertiary amine cation (TEAH+) to a tertiary amine (TEA) does not occur without an interaction with an anion (TFA–). An anion interaction with the amine increases its basicity, and as a consequence, it takes a proton from a cation either instantly (if the cation is freely moving) or with a small activation energy barrier of 2.62 kcal/mol (if the cation is interacting with another anion). The quantum chemistry calculations predict that anions are responsible for proton-exchange between cations and neutral molecules of a tertiary amine. Results from this study can assist the experimental choice of IL to provide enhanced proton conduction in PFSA membrane environments.